Derivatives of certain oxyalkylated phenol-aldehyde resins useful in coating compositions



jatented Sept. 16, 19552 UNITED STATES PATENT UFFICE 2,610,955Y Y ptRrvarrive-'s oF CERTAIN oXYALKYLAfrED rHENoL-ALDEHYDE RESINS USEFUL 1N comme ooMrosIrIoNs Melvin-De" Groote, University City, and Bernhardl Keiser, Webster Groves, Mo.,.assignorsto lBenzo.- lite. Corporation,l a corporation .of Delaware v.Norawing App'licationAuguSt2, 1.9482, Serial No. 425138 iaciaims. (omen-19) rlhis invention relates ten'lodif1ie'dv phenol-alde'# hyde'resinswhich are valuable as constituents ofv coating compositions, such as varnishes, enamels,

paintajjnks,'andtheilika being used in such corn-4 positionsn'in much thecsamfe way as thepresently used oil-modified resin bases, and includesvcoating;v compositions containing them 4as Ahlm-imm ing constituents. Thenew compositions; when used in coating compositions,` give coating-.mms which arer markedly 'resistant tol` weathering and which areA otherwise durable, are relatively inert toward, and compatible'with', pigments'and fillers, areY smooth, have `*high glosaare resistant towater'and'va-lkalifand: retain their hardness under c'oi'i-ditic'ms of* high humidity. AThey include compositions" whichv range in properties from com-positions which` have a relatively rapid dry-- ing; rate' to' compositions which have a.; slowerV orda-relatively slow dryingrate, and show Vvariations i-n properties similar to. those observed' in the short oil and the longoil alkyds.

The modified resins of the invention are obtained by the esterication of certain oxyalkylated phenol-aldehyde resins With the fatty acids of drying or semi-drying oils, and, advantageously, with a polybasic acid also. The phenolaldehyde resins which are used as starting materials for the production of the new products are prepared from difunctional (direactve) phenols` in which one of thereactive (o or. pl positions of the phenol is substituted by a hydrocarbon radical having 4 to 18 carbon atoms, in the substantial absence of trifunctional phenols, and aldehydes having not over 8 carbon atoms. By

substantial absence of trifunctional phenols, we mean that such materials may be present only in amounts so small that they do not interfere with the formation of a solvent-soluble resin. The actual amounts to be toleratedwilh product. of course, vary'withA the nature of the. other, componentsof the system; but in general the proportion of trifunctional phenolswhich is tolerable. in

the conventional reslnication procedures .illustrated herein is quite small. In experiments following conventional procedure using an acid catalyst in which We have included trifunctonal phenols in amounts of from 3% to about 1% or somewhat less, based on the difunctional phenols, We have encountered difficulties in preparing oxyalkylated derivatives of the type useful in the practice of this invention.

, These phenol-aldhyde. resins are' Yoxyallrylated with an alpha-betaV alkylene oxide having notl more ythanl.` carboni atoms, selected from theclass consisting; ofl ethylene oxide.. propylene oxide, bu-

. 2. tylene oxide, glye'de and@methylgllyeideJ insuch proportions that, on the average, for each; by droxylf-group of"1the resin, less ythan twoJmoleculesand' more than ene-half meleculeof alkyleneeX-ide isY used; with the proviso that at lleas-t' a-mapority. of the phenolic hydroxyll lradica-ls presen-t have their `phenoliehydrogen'replacedlby vthe hydroxyv alkylenev group, iso that, ofthe hydroxyl groups rtheoxvyalliylated" pred-uct, at least Y% arealco-f holic; "Advantageously, atfl'east'one'molecule of alkyleneoxide-is used'and all oflthe hydrox-yflsofA theoxyalkylfatedproduct are-aicoholic:

Tofpmduce-f-the newy compositions `the` oxyalkyl'- atedresins-arereacted with the fatty acids of drying-or semi-drying oils and', advantageously',

10.0%, leased. stochiometrical-ly von the wtotal.

(-nhenolim.ifanpiusalcoholic) hydroxyl--groups of theoxyalkylated resin; and, thezamiountfof the polyfbasie acid. may vary. 'from'.zero, to about 10%.... onthe same basis,withftheatotaiiof fatty acidland`V polybasieV aciolbeingifrom;about;50;% on the'l'same bassfto 1.00 based; on the: alcoholic L hydroxylsg. the phenolic AlfiydroXyls. being; non-reactive'.

.The phenoli-aldehydei resins. which. are=used-as start-ing` materials.vfor'therpreparationioflthe com;` positions of the. invention aref described. in our applications., Seria Noi.. '8130. ledLEebruary- 1.6,.

lai'andserial NQ.y 857311.. ledfFebruaryxlG, 19148;. both now al@anoLoIleli.` One type of.; these: resinsmay 4`be exemplified:l `vannidealized; simplification in the-following n formula;

. l." li.

Infthisrepresentation, nh represents a. numeral varying fromr 1- to r3 orl even more; provided.y .the resin isl fusible and organicv solvent-soluble,.jandl R is a hydrocarbon radical having at least 4' andV not over r8- carbon atoms. Such resins, when oxyalliylated vwith an alpha-beta alkylene oxide. having not more than-i-carbon atoms, in proportions varying from about one-half mole of alkylene oxide for each hydroxyl equivalent of the resin, to something less than two moles, give oxyalkylated resins having reactive alcoholiform hydroxyl groups, some or substantially all of which are subsequently esteried with the fatty acids of drying or semi-drying oils and, advantageously, also With a polybasic acid, to give the new compositions of the invention, which are outstandingly useful as constituents of coating compositions.

In producing the parent phenol-aldehyde resins, any aldehyde capable of forming a methylol or a substituted methylol group and having not more than 8 carbonatoms is satisfactory, so long as it does not possess some other functional group or structure which will conflict with the resinification reaction or with the subsequent oxyalkylation of the resin, but the use of formaldehyde, in itsucheapest form of an aqueous solution, for the production of the resins isparticularly advantageous. Solid polymers of formaldehyde are more expensive and higher aldehydes are both less reactive, and are more expensive. Furthermore, the higher aldehydes may undergo other reactions which are not desirable, thus introducing difficulties into the resinification step. Thus acetaldehyde, forexample, may undergo an aldol condensation, and it and most of the higher aldehydes enter into self-resiniflcation when treated with strong acids or alkalis. On the other hand, higher aldehydes frequently beneficially affect the solubility and fusibility of a resin. This is illustrated, for example by the different characteristics of the resin prepared from paratertiaryamyl phenol and formaldehyde on one hand and a comparable product prepared from the same phenolic reactant and heptaldehyde on the other hand. The former, as shown in certain subsequent-examples, is a hard, brittle solid, whereas the latter is softer and more tacky,

and obviously easier to handle in the subsequent A oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. vThe employment of furfural requires careful control for the reason that in addition to its aldehydic function, furfural can form condensations by virtue of its unsaturated structure. The production of resins from furfural for use in preparing products for the present process is most conveniently conducted with weak alkaline catalysts and often with alkali metal carbonates. Useful aldehydes, in addition to formaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde, 2-ethylhexanal, ethylbutyraldehyde, heptaldehyde, and benzaldehyde, furfural and glyoxal. It would appear that the use of glyoxal should be avoided due to the fact that it is tetrafunctional. However, our experience has been that, in resin manufacture and particularly as described herein, apparently only one of the aldehydic functions enters into the resinification reaction. The inability of the other aldehydic function to enter into the reaction is presumably due to steric hindrance. Resins produced with the use of furfural or glyoxal are, in our experience, dark in color and yuseful only for the production of final products to be used in `black or dark-colored coating compositions. Needless to say, one can use a mixture of two or more aldehydes although usually this has no advantage.

Resins of thekind which are used in intermediates for the compounds used in the practice of this invention are obtained with the use of acid catalysts or alkaline catalysts, or without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amines, and quaternary ammonium bases. It is generally accepted that when ammonia and amines are employed as catalysts they enter into the condensation reaction and, in fact, may operate by initial combination with the aldehydic reactant. The compound hexamethylenetetramine illustrates such a combination. In light of these various reactions it becomes difcult to present any formula which would depict the structure of the various resins prior to oxyalkylation. More will be said subsequently as to the difference between the use'of an alkaline catalyst and an acid catalyst; even in the use of an alkaline catalyst there is considerable evidence to indicate that the products are not identical where different basic materials are employed. The basic materials employed include not only those previously enumerated but also the hydroxides of the alkali metals, hydroxides of the alkaline earth metals, salts of strong bases and weak acids such as sodium acetate, etc.' Of the acids, oxalic acid appears to be the most useful. Hydrochloric acid tends to give dark products. Sulfuric acid is not usually useful, because it gives dark products and introduces sulfur, which is often objectionable in the nal product.

Suitable phenolic reactants include the following; Para-tertiary-butylphenol; para-secondarybutylphenol; para tertiary amylphenol; parasecondary-amylphenol; para-tertiary-hexylpheno1; para-isooctyl-phenol; ortho-phenylphenol; para-phenylphenol ortho-benzylphenol; parabenzylphenol; and para-cyclohexylphenol; paradecyl-phenol; para-dodecyl-phenol; para-tetradecyl-phenol; para octa decyl phenol; paranonyl-phenol; para-menthyl-phenol; para-betanaphthyl-phenol; para-alpha-naphthyl-phenol; para-pentadecyl-phenol; that of the formula 05H1 CHa(CH2)4lHl-CHr-CC5H1 v Hs I paraand ortho cetyl phenols; para cumylI phenol; phenols ofthe formula Ri-.C-Ri

in which R1 represents a straight chain hydrocarbon radical containing at least '7 carbon atoms and Rz and R3 represent hydrocarbon radicals the total number of carbon atoms attached to the tertiary carbon being at least l1 and not more than 17; and phenols of the formula Rx-CH in which R1 represents an alkyl hydrocarbon radlcal containing at least 'l carbon atoms in a straight chain and R2 represents an alkyl hydrocarbon radical containing at least 2 carbon atoms,

the total number of'. carbon atomsinl'ti and Rz being at least l1 and no tmore than 17; andthe corresponding ortho-para substituted; meta-,cresols and 3,5-xylenols.

The phenols herein contemplated for reaction may be indicated by the following formula:

t ...s k3 L in which R. is selectedtfrom 'the class consisting of hydrogen atoms and hydrocarbon radicals having at least .4 carbon atoms and not more Vthan 18'xcarb'on atoms, with the .proviso that one occurrence of R' is .the hydrocarbon substituent@ and the other two occurrences 'are -hydrogen atoms. and with the .further .provision that .one or both of ther3 and lpositionsfmay be methyl substituted. Y

The above formula possibly can be restated more conveniently in the following manner, to wit, that the phenol employed is of the following formula, with the Aproviso that R isa hydrocarbon substituent located in the 2,4,6 position, again with the provision as yto 3 or 3,5y methyl substitution. rIhis isy conventional nomenclature, numbering the various positions in the usual clockwise manner, beginning with'the hydroxyl position as `one: f

. The manufacture of thermoplastic phenol-aldehyde resins, particularlyfrom formaldehyde and a difunctional phenol, i. e., a phenol inY whichone of the three reactive positions (2, 4,16) has been substituted by a hydrocarbon group, and particularly by one having at least 4 carbon atoms and not more than 18 carbon atoms. is well known. As has been previously pointed out, there is no objection to a methylv radicaL provided it is present in the 3 or 5 position. A

The manufacture of thermoplastic or fusible phenol-aldehyde resins useful as intermediates for the kpreparation of products of theinvention is known. We refer to-our .Patent 2,499,370 for a description of the preparationof resins of this type and of the factors which .require considerael tionV in the selection of suitable resins. e. g., absence of trifunctional phenols in Aproportion .sufri-y cient to cause insolubilization, and the like. ,That patent also contains'a description of a procedure (column l2, line 9, et seq.) which we use .for determining vthe suitability of a phenol for preparing the products of the invention. We prefer, in examining phenols for producing products of the present invention to use a slightly vmodif-led test;

by preparing a resin from the'phenolandform-- aldehyde in excess (1.2 moles of formaldehyde per mole of phenol) vand using an oxalic acid catalyst, in the manner described hereinafterin Example la. If the resin so obtained is solventsoluble 'in any one of thearomaticor other solvents previously referred to, it is then subjected tooxyethylation. During oxyethylation a temperature is employed of approximately 1-50?. -to 165 C., with addition of at least 1/2 and Iless than 2 moles of ethylene oxide per phenolic hydroxyl. The oxyethylation is advantageously conducted so as to V.require from'a .few minuteszuptofto resin.

6F; 1.0..'hours'. .f the product so obtained-'is solventsoluble, the phenol is satisfactory fromthe standf-A point oftrifunctional phenol content. Whenfa'.

product becomes rubbers7 duringv oxyalkylation due tol the presence of a small-amount of itrireactivephenol, it may become extremely insoluble, and nolonger qualifies as being useful. Increase-V ing the size-.of the aldehydic-nucleus, forinstance;H using heptaldehyde instead offormaldehydqin* rapeseed oil, fish oils, and the like. VUseful ,polya basic acids (often used as anhydrides) includeV phthalic anhydride, 'succinic anhydride, IClocker adducts ofcrotonic anhydride such as the-adduct of crotonic anhydride andan unsaturated .fatty acid, Diele-Alder adductssuch asfthe maleic acide` terpeneand maleic, acid-pentadiene adductsdi-` merized fatty acids, adipic acid, diglycollic acid, and the like. The reaction ofthe oxyalkylatedresin with the acid or mixture of acids is an esterification, carried out in laccordance with customary procedure byheating to temperature ranging fr onfi-v 2400-to 250? C. for 4 to 24'hours. Heatinggtoltemperaturesfmuch higher than this may produce darkening of thel product. The esterification shoul'dbe carried out to substantialcompleteness.;

to give aproduct with a minimum acid number.,v

i. e.,9,\maximum of about 10, and,l advantageously, considerably less.

v Wherepolybasic acids are used along with fatty acids of drying orsemi-dryingv oils, further poly-y merization appears to'take place. As previously stated, the proportion of fatty acids usedis vfrom 20% to 10,0%, based on the total hydroxyls of the oxyalkylated-'resim and the amount ofpolybasic acid ranges from zero to aboutf'lO %A on the same basis, with the requirement that the total' amount of acid be stoichiometrically equivalent to at least 50% vof the hydroxyl groups of the oxyalkylated The preparation ofthe new productsof the i-n'- vention will be illustrated by the following specie fic examples, but the invention is not'limited thereto. For convenience, the examples have kbeen divided intol threegroups: 'Examples'la to 11'8a someof which are examples of Patent.'2,499,370 incorporatedlherein by reference, illustrating "the preparation of suitable parent resins; Examples 1b to 5b, and the table, the preparation of suitable'oxyalkylated Yderivatives thereof; and Examples 1c to 38e, the preparation of .suitable esteried derivatives, which are compositionsof the invention, and their compoundingto form coatingcompositions. f v' In the. production of the new compositions of the invention, including the preparation of the parent resin, the oxyalkylat'ed resin, and the. esterifled final product, duev precautions should be taken to avoid darkening. Thus, for the pro-i duction of light-colored products, all reactions should be carried outin equipment which does notv vtend to cause darkening, such as glass, enamel-lined, vstainless steel, or other suitable equipment, `with suitable precautions rtol exclude oxygen, ,for example, by blanketing the reaction mixtures .with--aninert gas, fsuch as carbondif.

oxlde, or nitrogen, or solvent vapor. Such precautions are those commonly used in the preparation of varnishes and products of that nature. Of course, for certain uses it is unnecessary that the compositions have a light color, as, forexample, where it is intended to produce a black or darkcolored final coating composition, andin such cases the precautionsto obtain'a light-colored product need not be used. l

The properties of the final products vary from those characteristic of the short oil type, that is. with relatively rapid drying rates, to those characteristic of the'long oil type, that is, with relatively slow drying rates. In general, the use of smaller proportions of the fatty acids of drying or semi-drying oils, and of larger proportions of polybasic acids tends to give products of the short oil type, while the use of small quantities or no polybasic acid and of relatively large proportions of the fatty acids, tends to give products of the long oil type. In general, the difference between the two is reiiected, not only indifferences in drying rates, Ibut also in differences in other properties. Thus, the short oil type tends to give hard films which in some cases may verge on brittleness, while the long oil type tends to give softer but more flexible and tougher films. The variation in properties between the two extremes is gradual, and compositions of the invention, with properties varying all the way from those characteristic of the short oil type -to the characteristic of the long oil type, may be prepared by appropriate variation in the proportions and amounts of the polybasic acid and the fatty acid. In general, decrease in the quantity ofA polybasic acid and increase in the quantity of fatty acid is reflected in an increase in drying time, `a decrease in hardness, and an increase in fiexibility and toughness of the films naliy produced. The short oil type is particularly adapted for the production of coating compositions lwhich are to be used for baked finishes. General characteristics of all of the compositions of the invention are their remarkable resistance to weathering and to alkali,.and their compatibility with pigments.

Example 1a Grams Tertiary butyl phenol (7 moles) A1050 Formaldehyde (371/%)1(6.5 moles) 525 Oxalic acid Wetting agent (Aerosol O. T.) 100% 2 Place all the materials in a 5-liter three-necked glass fiask fitted with an efficient glass stirrer, thermometer, and reflux condenser. Agitate continuously. Heat to 185 to 190 F. in 30 minutes, At this point an exothermic reaction may raise the temperature. Heat to 205 to 210 F. and hold for appearance of a thick, creamy mass, which will take place in about 45 minutes. Set the apparatus for distillation, and heat to 300 F. At about 260 to 275 F. an exothermic reaction will be observed. Hold the temperature at 290 to 300 F. until the resin has a melting point of about 235 F. on Parr melting point bar (Parr` Instrument Co., Moline, Illinois). The yield oi.' pale resin is 1100 to 1115 grams. The ball and ring meltingpoint is about 275 F.

Example 2a Grams Tertiary butyl phenol 1050 Hydrochloric acid (32%) 4 Formaldehyde (371/2%) 525 Aerosol Q. T. (100%) ,2

l'The procedure followed is that of Example la'. After 10 minutes at 300 F. the resin has a melt- Crude octyl phenol (7S-76% octyl phenol content)1 1670 Oxalic acid 8 Formaldehyde (BW/2%) 450 Aerosol O. T. (sulfated dialkyl succinate) 2 1 Contains traces of phenol, mineral spirits B. P. 90? to 135 C.V and water.

The procedure of Example 1a is variedvas follows:` Heat to 184 F.."Attain 200 F. in 30 minutes and hold for 11/2 to 2 hours. Distill to attain.

280 F. in about 11/2 hours. Distill slowly to attain 300.to 310 F. Hold until bar melting point is about 160 to 154 F. to attain ball and ring melting point of 190 to 205 F. Yieldis 1400 parts. v

` Example 4a parts of para-hydroxydiphenyl and 100 patsof commercial formaldehyde, with 0.7 gram Oxalic acid as a condensing agent, are heated in a closed container under pressure to a temperature, of about C. until the condensation is substantially complete. The water is then removed by he't'ing at reduced pressure. The product obtained by this procedure is a hard, clear, light-colored resinous material, melting. at about C. or higher and is readily soluble in tung oil and other fatty oils.

Ortho-hydroxydiphenyl can be substituted for the para-hydroxydiphenyl to yield a hard, clear, light-amber-colored material which melts at about 80 C., or the two can be mixed in varying proportions to give resinous products having any desired meltingpoint ranging from about 80 to about 150 C.

Example 5a 100 parts of para-hydroxy-diphenyl, 100 parts acetaldehyde and 1 part commercial hydrochloric acid are reuxed together. The mass is dehydrated to yield an oil-soluble product.

100 parts of para-methyl-cyclo-hexyl 'phenol and 48.4 parts of formaldehyde are refiuxed together in the persence of' 1.93 parts of oxalic acid for about 7 hours and dehydrated to a temperature ofA 120 C. A water-White non-heat-harden- :lng resin is obtained melting at about 287 C Example 8a. Y

100 partsrof octyl phenol is refluxed with 43.2 parts of formaldehyde andr 1.73 parts' of oxalic acid. i The resin separates in about 12 hours, and itis dehydrated to C. vThe resin obtained is soft, and, upon heating to 210 C., becomes brittle and about water-.white in color; it melts at about'163 F.

' Example 9a 100. partsof para-benzyl phenol is refluxed 8' 9 ho1n'swith'48-4'parts of formaldehyde and 1.93 parts of oxalic acid. .A brittle solid resin with a melting point' of about 1421" F. isV obtained.

Example 10a VCharge,1148 grams of p-terti'ary amylphenol, 525 grams of 37.2% formalin, 5 gramsv of oxalc uacid, and 2 grams of Aerosol ,0. T.into a threenecked glass flask equipped with the thermometermechanical glass stirrer and reflux condens-` er. Reuxthe mixture with stirring for 1.5 hours at 93-97 C.; then dehydrate by distillation at .110-150C. for 4.3 hours. About 454 grams of Water are removed. The yield, of hard, brittle,

reddish-yellow resin in one case was 1218 grams. Its melting point was 11G-123 C.

`Example 11u' vPounds Para-tertiary butylphenol 36.0 `Formaldelrxyde 36.9% 18.1 Xylene 38.9 Oxalic acd 0.2

Dioctyl ester of sodiumsulfosuccinic acid 0.06

cooled, and a stream/of nitrogen 'gas introduced concurrently. The remainder of the xylene'was added. The product, 76.2511bs. of pale tan slurry, contained 49.7% of, solid resin, of melting point 124-132?" C,l on a copper block. A total of 15.25 lbs.Y ofgwater was removed.

Example 12a Grams Para-tertiary butylphenol (1.0 mol'e) 150 Formaldehyde 37% (1.0 mole) 81 Oxalic acid 0.7

Monoalkyl (C10-C20, principally C12-C14) benzene monosulfonic acid sodium salt 0.8 Xylene '100 (Examples of alkylaryl sulfonic acids which serve las catalysts vand as emulsiers particularly in the form of. sodium `salts .include the' following:

v(R isian alkyl hydrocarbonradical having 1Zl4 carbon atoms.

/\/-SO3H v/ i tive andinterchangeable the following specific sulfonicfacids vor vtheir sodium saltszfA mixture of diand trlpropylated naphthalenelmonosulionic-acid; Vdiamylate'd .naphthalene -monosul- .'10 ionic acid; and nonyly naphthalene-monosulfonic acid.) 1 Y The procedure followed was that of Example 1a. Thephenol Was a flaked s olid. y The4 resin obtained in the operation above d escribed Was clear, light colored, hard, brittle, and had a melting point of i-165 C.

Example 13d The same procedure was followed l"as-in gthe preceding example, and thev materials usedthe same, except that the para-tertiary butylphenol Was replaced by anequal amount of para-secondary butylphenol. The phenol was agsolid of asomewhat mushy appearance, resembling-'moist cornmeal rather than 4dry flakes. ance of the resinwas substantiallyidenti-cal,with that of the preceding example. f

Example 14a :Grams Para-tertiary. amylphenol (1.0 mole) .1164 Formaldehyde 37% (1.0. mole) -81 Oxalic acidr" 510.7

benzene monosulfonicacid `sodium salt ;.A

The procedure lfollowed vwas the same af'slthat used in Example la, preceding. The phenol employed Was a flakedsolid.l The solvent-free resin Was light incolor, hard, brittle, with av'melfing point of 12S-140' C. ItWas xylene-soluble Example '15a ""The phenollemploy'ed (-1'64gram's) wa'sparasecondary amylphenol, which is a liquid, .theother ingredientsjbe'ing the same as in the preceding example. The p'rocedure followed was thesame ras that used in kllxample 1a, preceding-."The-solvent-free resin was 'hardand brittle, light in color and-Witha melting point ofSO-. C. l

Example 16a The phenol employed (164 grams) Was a commercially available mixed amylphenol containing approximately .parts of para-'tertiary amylphenol, and 5 parts of ortho-tertiaryamylphenol. It Was in the formof "a fused solid. Theother ringredients and the procedure employedwerthe same as those of Example :12a preceding."'The appearance of the resin was substantially the same as that of theV product of Example 14a.

Sometimes resins produced from ypara-tertiary amylphenol and formaldehyde in the presence of an acid catalyst show a'-slight insolubility in xylene; that -i,s wfhile completely soluble in hot xylene to give a clear solution, they give a turbid solution in cold xylene. Such turbidity or lack of solubility disappears on heating, cron the addition of diethylethyleneglycol;

We have never noticed this characteristic properlyV when using the commercial phenolof A'Example 16a which, as stated, is a mixture containing 95 para-tertiary amylphenol and 5% orthotertiary amylphenol., In fact, the additionfQf-. to 8%'of anorthO-SubStituted,phenohsuohasfortho-tertiary amylphenol,to any diiunctional parasubstituted phenol, such as the conventional Y employed.

.. Y `Example. 17a

The phenol employed (164 grams) vvas"v ortho- The appearv xylene.

11 tertiary amylphenol'which is a liquid. The other ingredients and the procedure followed were the same as those used in Example 12a, and the appearance of the resin was light amber in color and transparent. It was soft to pliable in consistency and xylene-soluble.

Example 18a The phenol employed (178 grams) was paratertiary hexylphenol. This is a solid at ordinary temperatures. The other ingredients and the procedure followed were the same as those used in Example 12a preceding, and the appearance of the resin was substantially the same as that of the resin of Example 14a. The solvent-free resin is slightly opaque in appearance, light amber in color, semi-hard to pliable in consistency, and xylene-soluble.

Example 19a The phenol employed was commercial paraoctylphenol. 206 grams of this phenol were employed instead of 164 grams of an amylphenol or 150 grams of a butylphenol and 150 grams of xylene were used instead of 100. Otherwise, the procedure and other ingredients were the same as those used in Example 12a. The solvent-free resin obtained was light amber in color, soft to pliable in consistency, and xylene-soluble.

Example 20a See Example 9a of Patent 2,499,370.

Example 21a The same procedure was employed as in Example 12a, except that para-cyelohexylphenol,

176 grams, was employed along with 150 grams of This phenol was solid. The resulting resin minus solvents was opaque in appearance, xylene-dispersible, amber in color, hard and brittle, with an approximate melting point of 170 C. It was suiiiciently curable to prohibit distillation.

Example 22a The same procedure was employed as in Example 12a, preceding, but using 198 grams of commercial styrylphenol and 150 grams of xylene. Styrylphenol is a white solid. The resin was light in color, hard and brittle, with a melting point of about 80 to 85 C.

The phenol, acid catalyst, and 50 grams of the xylene were combined in the resin pot previously described. The initial mixture did not include the aldehyde. The mixture was heated with Vstirring to approximately 150 C'. and permitted to reux.

The remainder of the xylene, 50 grams, was then mixed with the acetaldehyde; and this mixture was added slowly to the materials in the resin pot, with constant stirring, by means of a separatory funnel. Approximately 30 minutes Vwere required to add this amount of diluted aldeof para-phenylphenol.

hyde. A mild exothermic reaction was noted at the first addition of the aldehyde. The temperature slowly dropped, as water of reaction formed, to about to 110 C., with a reflux temperature being determined by the boiling point of water. After all the aldehyde had been added, the reactants were permitted to reflux for between an hour and an hour and a half before removing the water by means of the trap arrangement. After the water was removed the remainder of the procedure was essentially the same as in Example la. When a sample of the resin was freed from the solvent, it was light in color, semi-hard or pliable in consistency, and xylene-soluble.

Example 26a Example 27a The same procedure was followed as in Example 25a, except that the 150 grams of paratertiary butylphenol were replaced by 164 grams of para-tertiary amylphenol. The final solventfree resin was clear and dark red inv color. It was xylene-soluble and semi-hard or pliable in consistency.

Example 28a The same procedure was followed as in Example 27a preceding, except that the para-tertiary amylphenol was replaced by an equal amount of para-secondary amylphenol. The appearance of the resin was substantially identical with that of the resin of the preceding example, except that it was somewhat morefluid in consistency and slightly tacky.

Example 29a The same procedure was followed as in Example 27a, except that the amylphenol employed was the phenol described in Example 16a. The appearance of the resin on a solvent-free basis was substantially the same as that of Example 2 a,

Example 30a The same procedure was followed as in Example 27a, except that the amylphenol employed was ortho-tertiary amylphenol. The resin on a solvent-free basis was transparent and lightcolored; it was soft to tacky in consistency and xylene-soluble.

Example 31a The same procedure was followed as in Example 25a, except that the 150 grams of paratertiary butylphenol were replaced by 206 grams of commercial para-octylphenol. The solventfree resin was pale in color, soft to tacky in consistency, and xylene-soluble.

Example 32a The same procedure was employed as in Example 25a, except that the 150 grams of paratertiary butylphenol were replaced by grams The resin produced was at least dispersible in xylene when hot, giving the appearance of solubility. When the solution cooled, obvious separation took place. For this reason 100 grams of diethyleneglycol diethylether r3 were added to theenishedresin mixture, when licitfso as to give a suitable solution when cold.

Asmall sample was taken before vaddingfthe diethyleneglycol diethylether, andlthexylene `was ievaporatedin order toY determine the character-,of ftheresin. The solvent-:free resin was light in .color. vIt was -softand pliable in consistency.

Example 33a The same procedure was followed asin EX- ample 25a, vexcept that 176 grams ofpara-cyclohexylphenol were,employed` instead of the paratertiary butylphenol. Thesolvent-,free resinwas clear, light in appearance, soft to pliablein con-'- sistency, and xylene-so'luble;

Example 34a The same procedure was followed as in Exf ample 25a, except that thezphenol employed was commercial styrylphenol and the amount ena-- ployed was 198 grams. The resin was soft-topliable, light in color, vand,-xylenesoluble.v

Example. 35a

, Grams Para-tertiaryamylphenol (1.0 mole) 164 Heptaldehyde (lfmole) 114 Oxalic acid 2 Xylene 100 The procedure employed was essentially the same as in .-thelExample f25a, vwhere .acetaldehyde was employed, but ,with the Vdiierence that due to the fact that the particular aldehyde was a higher-boilingzaldehyde it 'was notnecessary to dilute it with the xylene. For this reason all the xylene was added to the initial mixture, and the higher-boiling 'aldehydewas added by means of a separatory funnel. Thus, the phenol, acid catalyst, and solvent were combined in a resin pot by the same procedure used as in Example 25a. The resin, after removal of the solvent by distillation, was clear, amber in color, had a soft, tacky appearance and `was lXylene-soluble. I

Example 36a y. Grams Para-secondary butylphenol (1.0 mole) 150 Heptaldehyde (1.0 mole) 114 Oxalic acid 2 Xylene 100 The same procedure was employed as inExample 35a. The'solventafree resin had Vlphysical characteristics smilarto .those of the resin of Example 35a.

`lilarcmtple 3 7a Grams Para-tertiary 'butylphenol v(1,0' mole) 150 Heptaldehyde (1.0 mole) 114 Oxalic acid 2 Xylene 100 This resin was yprepared `as in Example 35a preceding, with the resulting solvent-free resin being of a clear amber color, semi-hard or pliable, and xylene-soluble.

Example l. '38a y Grams Para-phenylphenol (1.0 `mole) 170 .Xylene 100 VI'herre'sin was prepared as in'Example 3'5a.

"v The 'solvent-free, resin was' slightly opaque, soft Kto iiiuid, and suciently `xylene-Idi'sper'sible to permit .subsequent oxyalkylation. Y

Example. 39a 5 Y Grams Para-cyclohexylphenol A(3.0 moles) 528 Hepta'ldehyde .(3,0 moles) 3,42 Oxalic acid Xylene 500 This resin, made as ,in ,Example -a, in ,solvent- 'free form .was clear., Aamber `in color, semi-.softto pliable andxylene-.soluble Example 40aY f Grams .laraetertiary amylphen'ol (1,0.Inole)l i164 Benzal'dehydelfl mole) '106 Oxalic acid. 12 Xylene :This resin, made as in Example 35a, in solventfree form was clear, hard, (brittle, `hadrammelting pointcf 16o-165'? C.., and was .xyleneesolublei Example 41a Grams Parafsecondary butylphenol mole) .(150 :BenZaldehyde mole) A 10 ',-Oxalic `:ac-id g f2 Xylene 100 This resin, made following the'procedure ernployed in Example 35a, in .solvent-free form was clear,l light in color, semi-hard or pliable and xylene-soluble.

Example 42a y Grams Para-tertiary bui'fylphenol` (1:5 moles) 225 :Benzaldhyde -(1.5 pieles) j 159 Oxalicracid i 3 lXylene :200

The above reactants were. .combined by the procedure of Example 35a. The solvent-free 'resin was a clear, hard, brittle, light amber colored resin, which was xylene-soluble, andhad amelting point'I of IBO-185 C. It was to some degree heat-curable.

Example 43a Grams Para-phenylphenol (1.5 moles) 255 Benzaldehyde (1.5 moles) 159 Oxalic'acid 3 -Xylene 290 'i YThis/'resin was `made as in Example 35a. The resulting solvent-freev resin-was clear, light,\h`ard, and brittle, lwitha melting point of 20D-205 C. It was somewhat heat-curable, and almost completely soluble in xylene, with some insoluble 'inaterial which was dispersible. It was suitable yfor subsequent oxyalkylation.

Example 44a Grams ,Para-cyclohexylphenol (3.0 moles)v 528 Benzaldehyde (3-.0 moles) ,318 .Oxalicacd 6 xyiene .50c

This resin, formed by combining the above reactants accordingito the procedure employed in `Example 35a, was hard, brittle, xylene-soluble,

light incolor, and had a melting point of l65-170 C., with .a tendency towards being heat curable.

Example 45a GraniisA Eara-ftertiary'amylphenol (1;0 mole) 164 rzrcpionaldehyde Y96% .(1.0 mole) 60.5 Oxalic acid f- `Y A2 Xylene l15() The above reactants were combined according Ato the procedure followed in Example 35a. The

resulting solvent-free resin was'clear, light amber :in color, soft to pliable, and xylene-soluble.

This resin was prepared according to the procedure employedin Example 35a. The resulting solvent-free resin was clear, soft to iiuld, light amber in color, and was xylene-soluble.

Example 47a Grams Para-tertiary butylphenol (1.0 mole) 150 Propionaldehyde 96% (1.0 mole) 60.6 Oxalic acid 2 Xylene 100 This resin was prepared according to the procedure employed in Example 35a. The resulting solvent-free resin Was clear, amber in color, xylene-soluble, hard and brittle, and has a melting point of 80-85 C.

Example 48a Grams Para-phenylphenol (3.0 moles) 510 Propionaldehyde, 96% (3.0 moles) 182 Oxalic acid 6 Xylene 500 Example 49a Grams Para-cyclohexylphenol (3.0 moles) 528 Propionaldehyde 96% (3.0 moles) 182 Oxalic acid 6 Xylene 500 'Ihe resulting resin, prepared according to directions in Example 35a, when solvent-free was clear, light in color, xylenesoluble, hard and brittle, and had a melting point of 84-90 C.

Example 50a Grams Para-tertiary amylphenol 164 2-ethy1-3-propy1 acrolein 126 Oxalic acid 2 Xylene 100 The procedure employed was the same as for the use of heptaldehyde, as in Example 35a. The resulting solvent-free resin was amber in color, and soft to fluid in consistency. It was xylenesoluble.

Example 51a Grams Para-tertiary butylphenol 150 2ethyl3propy1 acrolein 126 Oxalic acid 2 Xylene 100 The procedure employed was the vsame as for the useof heptaldehyde, as in Example 35a. The appearance of the resin was the same as the resin ofthe .Example 50a.

116 Example 52a ,v

. Grams Commercial para-octylphenol 206 2-ethyl-3-propy1 acrolein 126 Oxalic acid 2 Xylene 100 The procedure employed was the same as for the use of heptaldehyde, as in Example 35a. The appearance of the resin was the same as the resin of Example a.

. Example 53a see Example 42a of Patent 2,499,370.

i y Example 54a See Example 43a of Patent 2,499,370.

. Example 55a See Example 44a of Patent 2,499,370.

Example 56a See Example 45a of Patent 2,499,370.

Example 57a See Example 46a o f Patent 2,499,370.

Example 58a See Example 47a of Patent 2,499,370.

Example 59a See Example 48a of Patent 2,499,370.

Example 60a See Example 49a of Patent 2,499,370.

Example 61a` See Example 50a of Patent 2,499,370.

Example 62a See Example 51a of Patent 2,499,370.

Example 63a See Example 52a of Patent 2,499,370.

Example 64a ASee Example 53a of Patent 2,499,370.

Example 65a See Example 54a of Patent 2,499,370.

' y Example 66a See Example 55a of Patent 2,499,370.

Example 67a See Example 56a of Patent 2,499,370.

Example 68a See Example 57a of Patent 2,499,370.

Example 69a see Example 58am Patent 2,499,370.

Example 70a See Example 59a of Patent 2,499,370.

I Example 71a See Example 60a of Patent 2,499,370.

Example 72a Hg. The resulting resin was hard, brittle, amber colored, and had a slightly higher melting point than the'resin prior to vacuum distillation, to wit,

145 C. It was xylene-soluble. The molecul'ar Weight, determined cryoscopically'usingbenl' zene, was approximately 1400;" '5

This resin was obtained by the vacuum distillation of the resin of Example 19a. Vacuuinfdistillation was conducted up' to 225 C. at 25 mm. ",Ihle'rr resulting resin was xylene-soluble,y hard, brittle, reddish in color, with* a melting point' of lfm-145 C. Note that 'this resin, prior :to Vac-l uumdistillation, was soft to pliable in consistency.

u V Y Example74ad u 'u 4 e lThis resinlwas lobtained by the-vacuum distillation of the resin of Example 21a. Vacuum dis`l tillation was conducted up to 225 C.at 25l mm. The resulting resin was xylene-dispersible, soluble in ,a mixture of xylene and diethyleneglycol diethylether, brown vin colorand hard and brittle in nature, vIt had a melting point of, 180-185 C. This was moderately higher than the resin prior to vacuum distillation. 4 Y

.; Y Emamplea.

See Example flai oi' Patent 2,499,370.

Eramplehwa rllhis resin was obtained by the vacuum distil lation of the resin of Example 27o. Vacuum distillation was conducted up to 225 C'. at 25 mm. The resulting resin Vhad the salme physical characteristics as the undistilled resin except-that it was slightly more viscous. y u

" v' Y Ezmplewc This resin was obtained bythe Vacuum distillation of the resin of Examp1e-26a- Vacuum distillation was conducted up to 225 C. at 25 mm. The resulting resin was semi-hard to` pliable.

-- Example 78a This 'resin was obtained by the vacuum distiL-fv lation ofthe resin of Example 31a. Vacuum distillation was conducted up to 225l C; at' 25 mm. The resulting resi'n'1 was hardftoipliable.

In the immediatelyA preceding examples-"-de--- i Example. 7:91@ f 4 p See Example 68a oi Patent 2,499,370.

Example 80a y lVIenth'yl4 phenol, `technically u pure (0.1 l

mole) 232 Formaldehyde 37% V(1.0 mole) 81 Oxalic acid 0.7

Monoalkyl, (Clin-.Cza principally C12-C14.) benzene mohosulfonic acid' sodiumsalt Xylene 200 The procedure followed 'was that of Example la. The resin4 obtained was clear, amber in color, hard, brittle. and' had a melting pointof about 115-120C. Y f

18 Eample '81a l Gramsv Nonylphenol' (para) 3.0 moles 660 Formaldehyde 37% (3.0 moles) 243 Oxalic acid 3.2

Monoalkyl (Cio-C20, principally C12-C14) benzene monosulfonic acid-sodium salt 2.5 Xylene 300 vThe procedure followed was the same as that used in Example la. The phenol employedwas a heavy', sirupy liquid, largely or almost entirely7 para with possibly a small percentage of ortho present.V The solvent-free resin was clear, light in color andsemi-soft or pliable in consistency.

Example A82a u Grams Octadecylphenol (1.0 mole) 346 Formaldehyde 37% v (1.0 mole) '81 Oxalic acid 1.1

light amber in color.V

Example '83d j Grams Crude para-cumylphenol (1.27 moles) 268 Formaldehyde 37% (2.0 moles) 162 Oxalic' acidy 0.9 Monoalkyl (Cio-C20, principally C12-C14) benzene monosulfonic acid sodium salt 1 Xylene 250 i,The so-called ycrude para-cumylphenol was a comparatively high grade product containing 90% to 95% of the phenol and the impurities present were hydrocarbons with less than 1/2% of phenol (hydroxy-benzene). The phenol was a yellowish colored so1id,'having a` somewhat waxy appearance. The procedure followed was that of'EXample 1a. The resulting solvent-free resin was slightly opaque, amber in color and hard but not particularly brittle. It had a melting point of to 35 C.

" Eample '84a y Grams Para-decylphenol (1.0' mole) 234 Formaldehyde 37% (1.0 mole) 81 Oxalic acid 0.7

Monoalkyl (Cro-Cao, principally C12-C14) benzene monosulfonic acid sodium salt 1.2

Xylene 200 The procedure followed was the same as that used in Example 1a.. preceding. The phenol was a straw colored liquid having a little phenolic odor. "The solvent-free resin obtained was light in color and semi-soft or pliable in consistency.-

)Eixampley '85a Grams Para-dodecylphenol (1.0 mole) 262l Formaldehyde 37% (1.0 mole) 81 Oxalic acid 1.2

Monoalkyl (Cro-C20, principally C12-C14) benzene monosulfonic acid sodium salt 2.5

Xylene 250 The procedure followed was the same as that used in Example la. The phenol was a straw Example 86a See Example 74a of Patent 2,499,370.

Example 87a Grams Menthylphenol, technicallyvpure (1.0 mole) 232 Acetaldehyde (1.0 mole) 44 Oxalic acid 2 Xylene 100 The, phenol, acid catalyst, and 50 grams of the Xylene were combined in the reaction vessel. The initial mixture did not include the aldehyde. The mixture was heated with stirring to approximately 150 C. and permitted to reflux.

The remainder of the Xylene, 50 grams, was then mixed with the acetaldehyde; and this mixture was added slowly to the materials in the resin pot, with constant stirring, by'means of a separatory funnel. Approximately 30 minutes were required to add this amount of diluted aldehyde. A mild exothermic reaction was noted at the first addition of the aldehyde. The temperature slowly dropped, as water of reaction formed, to about 100 to 110 C., with the reflux temperature being determined by the boiling point of water. After all the aldehyde had been added, the reactants were permitted to reflux for between an hour to an hour and a half before removing the water by means of the trap arrangement. After the water was removed the remainder of the procedure was essentially the same as in Example 1a. The solvent-free resin was hard but not brittle, amber in color and had a melting point of about 50 to 55 C.

Eample 88a Grams Nonylphenol, para (0.773 mole) 170 Acetaldehyde (0.773 mole) 34 Oxalic acid 3 Xylene 75 The same procedure was followed as in Example 87a,' except that nonylphenol was used instead of menthylphenol. The solvent-free resin was amber in color and soft to pliable in consistency.

Example 89a Grams Octadecylphenol (0.5 mole). 173 Acetaldehyde (0.5 mole) 22 Oxalic acid 1 Xylene 75 The same procedure was followed as in Example 87a, except that octadecylphenol was used instead of menthylphenol, The solvent-free resin was soft to semi-brittle in consistency and reddish in color.

Example 90a Grams Menthylphenol (3.0 moles) 696 Heptaldehyde (3.0 moles) 343 Oxalic acid 6 Xylene 500 The procedure employed was essentially" the same as in Example 87a where acetaldehyde was employed, but with the difference that due to the fact that heptaldehyde is a higher boiling aldehyde, it was not necessary to dilute it with the Xylene. For this reason all the Xylene was added to the initial mixture, and the heptaldehyde was added by means of a separatory funnel. Thus,

20 the phenol, acid catalyst, and solvent were cornbined in a resin pot by the same procedure used in Example 87a. The resin, after removal of the solvent by distillation, was clear, light in color, had a soft, tacky appearance and was xylenesoluble. l

Example 91a g Grams Nonylphenol (1.0 mole) 220 Heptaldehyde (1.0 mole) 114 Oxalic acid 2 Xylene 150 The same procedure was followed as in Example 90a preceding. The solvent-free resin was dark amber in-color and semi-fluid or tacky in consistency.

Example 92a Grams Menthylphenol (1.0 mole) 232 Benza1dehyde (1.0 mole) 106 Oxalic acid 2 Xylene 150 The procedure followed was the same as in Example 90a. The solvent-free resin was semi-hard to pliable and light amber in color.

Example 93a l Grams Nonylphenol (1.5 moles) 330 Benzaldehyde (1.5 moles) 159 Oxalic avid 3 Xylene 200 The procedure followed was the same as in Ex- The same procedure was followed as in Example a 'I'he solvent-free resin was amber in color, semi-hard or pliable in consistency, with a tendency towards tackiness.

Example 95a Grams Nonylphenol 220 Propionaldehyde 96 (1.0 mole) 60.5 Oxalic acidA 2 Xylene 150 The same procedure was followed as in Example 90a. The solvent-free resin was amber in color and semi-fluid or tacky in consistency.

Example 96a Grams Nonylphenol (1.0 mole) 220 2-ethyl-3-propy1 acrolein (1.0 mole) 126 Oxalic acid 2.5 Xylene 100 The same procedure was followed as in Example 90a. The solvent-free resin was dark in color and soft to fluid in consistency.

Example 97a Grams Menthylphenol (1.0 mole) 232 2-ethyl-3-propyl acrolein (1.0 mole) 126 Oxalic acid 2.5 Xylene The same procedure was followed as in Example 90a.- The solvent-free resin was dark in color and soft to fluid in consistency.

Example 1.03a

See Example 90a of' Patent 2,499,370.

Example 10.4a

See Example 91a of Patent 2,499,370.

Example 105a A. duplicate of. theA resin described in Example 80awas prepared and. subjected todistillation. Distillation without vacuum was rst employed to eliminate the xylene. After the elimination of xylene the resin was subjected to vacuum distillation to 225 C., at 25 mm. Hg. The resulting resin was a hard, brittle, amberl colored resin, xylene-soluble and had a melting point ofv 145 to 150 C.

Example 106eA A duplicate of the resin described in Example. 81a was prepared and subjected .to distillation,

including vacuum distillation, in the same manner as describedin Example 105a. The resulting` resin was a clear, hard, brittle, xylene-soluble resin, amber colored, and had a melting point of 80 to 85? C.

Example 1'07a.

See Example 99a of Patent 2,499,370. 60

Example 1,13a

Asee Example Iooa of Patent 2,499,370.

Example 114a 65 Grams y Dodecylphenol. 262 Benzaldehyde 106 Oxalic acid l .i 2.5 Xylene 100 The procedure. followed was that of Example 87a. The solvent-free resin was clear, light in color, xylene-soluble, and` soft to sistency.

Example 115a f see Example roza of Patentmsasv Example 116a n ,"Grams M'onoa-lkyl (C1o-C2u. principally C12-C14) benzene monosulfonic aoidsodiumfsalt-; '1.5 Xylene 1. Q---.Lf 2005" The procedure followed was. that-of Example 1a., The resulting; product was light amber co1- ored resin` having a meltingpointof 115 110.1209 C.. The solvent free. resin was similar inappear ance. to the resin of ,Example a.

Example 117a 4Grams Para-tertiary' butyl phenol' (7.0 moles) li059.

All the materials wereplacedin .a3-liter threenecked glass lflask fitted with an. efficientstirrer,A thermometer and reflux condenser and agitated continuously. The mixture was refluxed for minutes at 88-92 C., at-Which rtime itbecame a thick, creamy mass.. It was dehydratedgby. distilling, at 97-162P C., y'for 5 hours. A total ofi 395 grams of water was removed. YieldwaslllZ grams of hard, brittle, yellow resin.,k dimming point 1132-126.e C..v i

Example 1'1'8a .1050. grams of.l p-tertiary butylphenol'.. 5.00l grams, of 39.7% formaldehyde, grams: ofoxalic. acid and 2 grams ofAerosol O. T.. are refiuxed,for'y 85. minutesat. 88-,92 C., andthen dehydrated by distilling at 97-148 C. for 5 hours. 403 grams of water in one case were removed. The product was a hard, brittle, yellow resin, meltingat 124127 C., yield 1093 grams.y l

In a` number of the foregoing examplesgphe# nols have been identied simply as: ,'nQnyL nel, or octadecyl phenol, or the like, v'vthout specific. design-ation of the position. of' substitue, tion or the structure of the substituent radical..

In such cases, the phenols. meant are eithe'the:

commercial products distributed under these names, or, if the. products arenoteommercially available, the products obtained byrcustomary'A syntheses from phenol, metacresol or 3,5-xylenol`;

andconsist mainly of the' para-substitutedfprod-L- n uct, usually associated withsome of tlieortliosubstituted product, perhaps averyl smalli'proh.` portion of meta-substituted material, somefimpurities, etc. Also it is tobe understood that all: of the products of the foregoing examples,"unles`s=. it is otherwise stated in the example, are soluble in xylene, at least to an extent suflicient to permit the use of xylene as the solvent inoxyalkylaton.

It will be noted that the resinsusedas parent7 materials, as illustrated by Examples 'la to 11872,'- are 2,4,6 (i. e., 2, 4 or 6) C4- to (lm-hydrocarborf substituted monocyclie phenol--Crto Cala-Idal hyde resins. Advantageous'ly thefresin moledule has 3 to 7 phenolic residues it may have-more. Most of the resins herein described'p'articullrjlff in the absence of a secondary heating step,=co`n tain 3 to 6 or 'l phenolic nuclei, with approximately 41/2or51/2 nuclei as` an average, basedilon molecular weight determinations', following-the.; cryOSQQPiQ pr'svedure described. in curatent;

23 2,499,370. In the appended claims we have used low-stage to mean 3 to rIrunits based on average molecular weight. These give the most desirable nal products.

The oxyalkylation of the resins to produce the oxyallrylated products from which the products of `theY present invention are prepared is carried out in a manner described in our- ,svaidPatent 2,499,370, except that the extent of oxyalkylation is limited to from 1/2 to 2 moles of alkylene oxide per phenolic nucleus, advantageously .about 1 mole or slightly more being used, so that the oxyalkylated products are substantially free from phenolic hydroxyl groups. In Examples 1b to 5b, and the table which follows, directions are given for the production of the oxyalkylated intermediate which are subsequently esteried to produce the iinal4 compositions of the invention. Because of advantages whichfollow from the use of ethylene oxide, partly because of its low cost and partly because of the excellent results it gives, most offthe examples relate to oxyalkylation with yethylene oxide. However, oxyalkylation with propylene oxide, butylene oxide, glycide and methylglycide, gives substantially equivalent products. Glycide, if used, should be handled with great caution.

. Example 1b y443,50 grams of the resin of Example 11711 dissolved in 4350 grams of hot xylene were placed in a stainless steel autoclave with 19 grams of sodium methylate and 1200 grams of ethylene oxidefand the mixture was heated to 150 C.,-

when a drop in pressure was noted. The maximum pressure observed during the operation was 120 p. s. i. gauge. vHeating was continued until the temperature reached245" C., when' the heat was shut off and the autoclave allowed to cool. Time above 150 C. was 1% hours. The product obtained was a light tan' semi-crystalline mass.

Example 2b A The' same reactants vand procedure were em-1 ployed as in Example 1b, preceding, except that propylene oxide was used instead of ethylene oxide, in equivalent proportions. The nal product was verysimilar to the product of Example 1b.

Butylene oxide, similarly used, 'gives a similar product.

Example 3b `'.l'hegsame reactants were employed as in Example 1b,except that the equivalent amount of.. glycide -was used instead of ethylene oxide, the;

reactionwas conductedwith extreme care and the glycide was added in small proportions, followed by the allowance of time for reaction beforethe addition of the next portion. Again the product was similar to the product of Example `1b in appearance.

' Example 4b 594 grams of the resin of Example 10a dis;

solved in 396 grams of xylene and 2.4 grams oi' sodium methylate and 175 grams of ethylenev grams of sodium methylate, Were charged into the stainless steel autoclave- The maximum temperature observed was 198 C., and the maximum pressure 101 p. s. 'i'.'gauge The reaction time was 3 hours. Thexylene-containing'reaction product was a semi-crystalline mass.

In the table which follows are given the data for the oxyethylation'with amounts` of ethylene oxide ranging from about one-half mole to something less than two moles per hydroxyl equivalent (of theresin) of a large number of the resins, the production of which is illustrated in Examples 1a through 118a.

The rst column (A) gives the example num- Iber where the production of the resin is described; the second column (B) gives the weight, in grams, of the resin which is oxyethylated; the third (C), the weight, in grams, of the solvent in the solution; the fourth (D), the weight, in grams, of catalyst (sodium methylate) used; the 115th (50,5115 amount 5f ethylene oxide added, in grams; the sixth (F), the maximum temperature used; the seventh (G), the maximum pressure observed, in vpounds pei` square inch gauge;

' and the eighth (H), the time of reaction, Vin

hours.

.4 B c D E F G n 175 1.8 44 150 155 2.5 175 1.8 44 130 135 4 175 1.8 44 150 105 2 175 1.8 44 150 100 2.5 190A 1.8 44 155 150 4 218 1.8 44 155 155 4 132 1.8 44 150 150 2.5 188 1. 9 44 155 120 v4. 5 210 2.1 44 155 125 5 175. y 1.8 44 155 145 3.3 175 1. s 44 148 14s 3. 5 175 1.8 44 140 125 5 175 1.8 44 150 140 5 1. 9 44 155 13o 4. 5 4 -.100. 1. 9 44 140 05 1 190 41.8 44 145 115 3 1. 9 44 130 140 2. 5 232 2.3 44 130 130 3 232 2.4 73 14o 125 4 232 2.3 31 145 135 4.5 195 2.0 44 150 125 3 202 2.0 44 135 135 1 224 2.2 44 135 145 4 250 2.5 44 145 130 3.5 250. 2.5 33 140 125 3 250 2.5 135 3 246 2.4 44 140 130 3 245 2.5 44 145 135 3 255 2. 7 44 145 133 0. 5 272 2.7 44 150 140 0.a 252 2.5 44 135 95 2.5 238 2.4 44 144 150 4.5 238 l2.4 44 150 125 1.5 258 2.5 44 135 90 0.5 254 2.5 44 135 150 5.5 204 2.0 44 142 92 4.5 190 1.0 44 144 153 3 190 1.9 44 125 120 2 210 2.1 44 140 130 0.8 215 2.2 44 142 120 2 272 2. 7 44 13s 133 5. 3 258 2.5 44 142 132 1.5 314 3. 1 44 148 140 3. 5 242 2.4 44 113 107 2 221 2.2 55 120 110 3 175 1.8 44 155 150 2 152 1.5 44 140 150 2 152 1.5 59 145 155 2 152 1.5 29 145 150 2 182 1.8 44 150 145 2 188 1.8 44 155 150 2.5

A B C D E F G H 162 162 1.6 44 150 140 2 176 176 1.8 44 155 150 2 162 .162 1. 6 44 155 145 2 218 218 2. 2 44 16() 150 3 218 218 2. 3 .79 v 150 145 2.5 218 218 2. 2 35. 165 155 3. 5 176 176 1. 8 44 160 155` 2 162. 162` 1. 6 44 150 140. 2 182 `182 1. 8 44 155 15()` 2 188 188 1. 9 44 15() 130 2. 5 162 162 .1. 6 l 44 -15() 145 v v2 176 176 1. 8 44 150 145 2 162 '162 1. 6 44 '150 140 2. 21.8 218 2.2 l44 155 150 3. 176 176 1.8. 44 150 140 2 176 176 1. 8 44 160 155 '2 218 .218 2. 2 l44 .160 150 4..5 188 188 1.9 v 44 150 135 4 182 182 158 '44 145 1'40 '2 190 190 1..9 vv44 15() 140 '.4 176 176 1. 8 44 .155 145 `5 232 232 2. 3 44 135 130 3 176 176 1.8 ".44 140 106 3 244 244 2. 5 44 150 Y 140 1A '244 f244 u 2. 5 23 i155 145 1. 5 244 '244v 2.'5. 62 ,145 '135 I 0. 8 232. 232 2. 3 44 ,140 100 0. 8 232 232 2. 3 85 135 1l() 1.0 232 232 2. 3 22 150' 120 1.'.5 358 35S 3. 6 44 150 140 Y 2 358 358` 3.*6 79 145 125 3 358 358 3. 6 24 140 120 3 224 l224 2.32 44 l 130 162 0. 5 246 246 2. 5 44 158 185 3.5 274, 274 42. 7' 44 i 152 ,190 1. 3 .274 274 2. 7- 84 165 '170 -1 2 274 274- 2. 7 '26 '170 R 180 2 232 '232 2. 3 44 138 '.82 u 1 258 258 2.6 114 '1'50 140 2 246 .246 2. 5 -44 .145 140 I 3 '246' 246 2. 5 75 145 2 372 372 A3. 7 44 160 145 '2 372 '372 '3. 7 '34 Y 155 135 4 372 372 '3. 7 22 160 140 3 328 328 3. 3- 44 j 144 133 '10 V316 316 3.2` 44 140 130 2 i320 320 -3. 2 44 135j 130 5 v308 308. 3. 1 44 140 135 i 6 328 328 3. 3 -44 144 115 .2. 5 340 340 3. 4 '44 '150 '140 V3 244 244 2. 4 44 140 130 4 232 -232 2. 3 44 150 95 1. 5 232 232 2. 3 44 125 130 5 S298 .298` v3.0 u44 .135 l 145- 1 Y ln general, `the-appearance of -thefproducts the presence of' the solvent, was that of a viscous liquid or 5a semi-crystallinefmass, vary-ing lin color from light tan to'reddish amber. 'For some ,sub-`- sequent applications -of 'our' materials, separation of the product from the vsolvent is unnecessary'.y For example, in using our nished intermediates as starting materials incertain esteriiication-reactions, the ,products were -not .separatedlirom the A.solvent prior to .admixture wththe :desired acids for .esterication. Y v

Conversion .of these oxya'lkylated products 'into the .esteried compositions .of the .invention involves adnixture of .the oxyalkylated product with lthe selected amount .of .acid or fmixtureof acids. followed by heating to .esterifgyng tem-V perature for a suiicient time to substantially completely esterifythe acid.` yIf theoxyalkylated product' is producedin admixture with .a solvent, it 'is unnecessary to remove the solvent prior Ato the addition of the acid as the solvent will be 26 vantageously about'235" C., are used for esterication. lThe time required varies from about 4 Vto24 hours. Completion is shown by testing the acid number-a value below about 1.0 being required, .or'by astroke cure test'(cf. D'Alelio,Ex perimenta'l Plastics Vand Synthetic Resins, r194e,

seconds or less usually indicating completion. Products with longer cure times, e. g., 30 seconds, are often satisfactory. Reference herein to cure time is to this test carried out in this way. During esterication, the reaction mass must be protected-from the air, as -by blanket- -ing with ani-nert'gas, if a light 'colored product is to be obtained.`

In preparing coating compositions, the Vnew `esteried products are compounded with a solvent or solventsfpig'ments andv driers in the Vusual way. Varnishes are prepared without pigments, enamels Lwith pigments. Inks are prepared with pigments. The new products, for use `in pai-nts, are Vcompounded with drying oils. Preparation of pigmented products is comparatively easy, because pigments are readily ground into the new products. Such compounded products have excellent shelf life, good spreading properties, give smooth, glossy iilms, which are weather resistant, durable, alkali and water resistant, retain their hardness even under conditions fof-high humidity, and have ,an excellent lbalance of hardness, toughness ,and flexibility.

`The following examples, 1c to 38e, illustrate the'production ofnew esteried compositions of the invention, Vand'nal coating'compositions in `which they are incorporated, by 'the lesterication of oxy-alkylated products 4of the type illustrated in VExamples. lfb throughv 5b, and theforegoing table, with the-use of varyingpr'oportions of -fatty acids, and varying proportions of polybasc acids, and the 'production 0f Dloductsmranging from fthe jshortj oil type to the long oil type. Pigmented as-well Aas unpigmented [coating .compounds"aref-als lustrated.l

Y, Example `1c 190.5 ,grams fofA the 1oxyethylated productof Example-4b in ,38 `gramsfof, ,xylene were mixed with 42 grams of lnseed oil fatty acids and 22.2 grams of phthalic anhydride. Themixture was heated to 190 C. for 45 hoursin a lthree-necked glass flask ywitha-,mecl'iariical glass stirrer, .to a stroke clureV .test time Aof 30 seconds (curev plate 'at 200,"v C.') and an acid number of 18.3. A 50% xylenesolution -of the product had a .viscosity of approximately 05.y centipoises. .1t gave fn'onbrittle lmspf satisfactory color. 160% xylene solution wa .a satisfactorycoaitinglcomposition.

It 'was .ctfniedium oil type.

fcation. Temperatures of V1200" toJ 250 vfC., "ad- .1134.5 grams-of a'x-ylene solution of the oxyethylated .resinof vExample 4b, containing 596:5 gra-ins fof. resin, Vwere reacted with '146.7 grams jof linseed oil fatty acids and 1.2.3 grams of phthalic anhydride by heating ,-to-'-190 C., for 2.5 hours and at 220 to 4225" C. for `4 hours, to a stroke cure time .of "30 seconds (200 C.) and anacid value' of v'1.6.` A' 5,0% xylene solution -of- 'thezproduct hada viscosity -of approximately Vffii-.centipoises. "The 'productvr gave l10n-brittle g v:Films which `were As,atisfactory vin color. @1t 1 was vofmedium .ou type.

-xylene solution were mixed with 37.2 grams of linseed oil fatty acids and 14.7 grams of phthalic anhydride'and heated to 190 C. for 2.5hours, and at 220 to 225 C. for 4 hours, to a cure time of 18 seconds, and an acid value of 21.8. A 50% xylene solution of this product had a viscosity of about 200 centipoises. A 70% solution was a satisfactory coating composition. Films prepared from this product were satisfactory as to color and flexibility. It was of medium oil type.

Example 4c 180 grams of a xylene solution of the oxyethylated resin of Example 5b, containing 47% solids, was mixed with 24.7 grams of phthalic anhydride and 46.7 grams of linseed oil fatty acids and heated to 200 to 240 C.. to a cure time of 20 seconds and until an acid value of 5.4 was obtained. The period of time was about 8.1 hours. A 59% xylene solution of the product had a viscosity of about 50 centipoises. Films prepared from this product had a very pale color, become dust-free in air in 14 minutes and tack-free in 5.8 hours. It was of medium oil type.

Example 5c 24 pounds of a 46.5% slurry of the oxyethylation product of the resin of Example 11a (8.25 pounds resin plus 2.9 pounds ethylene oxidesee table) were reacted with 2.1 poundsof phthalic anhydride and 6.6 pounds of linseed oil fatty acids, and heated for 25 hours at 206 to 249 C., to a cure time of 16 seconds and an acid number of 3.1. A 52% solution of this esteriied product in xylene had a viscosity of 78 centipoises and a Gardner color of 13. The clear lm of this product had a dust-free time of 23 minutes and a tack-free time of 1.3 hours and produced a film of extremely high gloss. This film showed no effect from weathering after exposure for the equivalent of two years in'an accelerated weather machine, and would not dissolve in 3% caustic after submersion fr1504 hours. This product was pigmented with titanium dioxide at a vehicle-to-pigment ratio of 1:1, to produce high gloss weather-resistant enamel which had a dust-free time of 30 minutes and a tack-free time Yof one hour. It was of medium oil type.

Example 6c 28 pounds of the same resin slurry -asin preceding Example -c were reacted with 2.3 vpounds phthalic anhydride and 7.3 pounds of soybean fatty acids. The materials were heatedforV hours at 215 to`241 C., to -a cure time of 30 seconds and an acid number of less than A1. This esterified product, in :3.151% solution in xylene, had a viscosity of 100 centipoises and aGardner color of 14. The clearillm produced byv this product had a dust-freetime of 15 minutes and a tack-free time of 2.3 hours. Pigmented with titanium dioxide at a vehicle-to-pigment ratio of 1:1, it produced a high gloss enamel withl high alkali and weatherresistance. It was of medium oiltype.v i 1 Example 7c 23 pounds of the same resin slurry as in preceding Example 5c were reacted with 1.2 pounds of phthalic anhydride and 9.6 pounds of linseed oil fatty acids. The materials were heated for 28 hours at a temperature of 226 to 238 C., to a cure time greater than 120 seconds and an acid number of less than 1. A 60% solution of this esterified product in xylene had a viscosity of 62 centipoises and a Gardner color of 11. Clear 428 films sprayed from this solution had a dust-free time of 4 hours and a tack-free time of 6 hours. It was of long oil type.

Example 8c 26 pounds of the same resin slurry as in preceding Example 5c were reacted with 2.2 pounds of phthalic anhydride and 3.4 pounds of linseed oil fatty acids. These materials were heated for 5 hours at a temperature of 200 to 249 C., to a cure time of 5 seconds and an acid number 'of less than 1. A 47% solution of this esterfled product in xylene had a viscosity of 550 centipoises and a Gardner color of 10. Clear films sprayed from a 42% solution of this esteried product had a dust-free time of 13 minutes. Pigmented with titanium dioxide at a vehicle-topigment ratio of 1:1, it gave a fast drying, high gloss enamel, with a dust-free time and tackfree time of 22 minutes. Clear andpigmented lms of this product did not dissolve in 3% caustic when submerged for 3 weeks. It was of short oil type.

Example 9c 30.4 pounds of a 22% xylene solution of the cold-xylene-soluble portion of the oxyethylated product described in Example 5c preceding were reacted with 12 pounds of phthalic anhydride and 3.7 pounds of linseed oil fatty acids for 141/2 hours at 210 to 239 C., to a cure time greater than 60 seconds and an' acid numberof v7.2. A 51% solution of this product in xylene had a viscosity of 52'centipoises. Films cast from a solution of this resin showed extremely high alkali resistance, with no noticeable change after 17 hours of submersion in 3% caustic alkali and remained clear after 3 weeks of submersion. It was of medium oil type.

Example 10c 8.4 pounds of the cold-xylene-insoluble portion of the oxyethylated resin described in Example 5c were reacted with 1.4 pounds of phthalic anhydride and 4.3 pounds of linseed fatty acids. The materials were heated for 6.5 hours at 224 to 230 C., to a cure time of 15 seconds and an acid number of 9. A 54% solution of this esteried product in xylene had a viscosity of 144 centipoises. Clear films sprayed in xylene solution had a dust-free time of 17 minutes and a tack-free time of 3 hours, and a Sward hardness of 45 after 24 hours of air drying and 50% relative humidity. Pigmented with titanium dioxide at a 1:1, vehicle-,to-pigment, ratio, this resin produced a high gloss, fast drying enamel which was unaffected by submersion in 3% sodium hydroxide for threerweeks. It was of'short oil type.

Example 11e "Ihe resin of Example 1a, oxyethylated with an equimolar proportion `of ethylene oxide (see table) is heated with an equimolar proportion of tung oil fatty acids, the amount of oxyethylated resin being 206 grams and the amount of tung oil fatty acids being 270 grams. Thereaction mixture lis heated to about 200 C. for several hours,`until the acid number is less than 10. The resulting product is of the long oil type.` A, product'similarly prepared b ut using '140 grams of tung o il fatty acids is, Isomewhat ,similar in properties, 'but gives Vlighter colored, harder filmsi1 g f I vErcamplelZc y l A, The productrobtained in accordance withthe precedingexample by using the smallerfquantity of tung oil, i. e., 140 grams, is heated to 200l 1Q., for several hours With12l grams of maleic anhydride, giving a product with low acid number Whichforms hard, clearfilms.

. Erdmivleflc f. -.Theprocedure of Example llc isfrep'eated, L'ising;A linseed -oil fatty acids 'instead of tung-'oil fatty v.acidsinthe same amounts. `The resultingr products givev lms which are somewhatsuperior toithbse ofthe products of-Examp-lellcyiand:the products show less tendency tofgelfv Thehuse `oi equivalent .proportions of dehydrated -.'c'as'tor.i oil fattya'cids .instead of thetung or -linse'ed-=fatty acids gives products similar to thoselobtaned with the use of linseed fatty faci'dsf l i Eamnle 14e A Diels-Alder adduct prepared from linseed oilY and rmaleic anhydride kin the conventional ir'iannerQand is' jthen reacted in equimola'rproportions with the same o x'yethylated derivative of the'resih of Example 1a used in' E-Xample` 'llc,` 206 parts of the oxyethylated resin being used with f95i0 parts of: the Diels-#Alder adduct'. The reaction was carried out byheating 'for 1'2 hours at about 200 C., to produce condensatio'nlfllhe resltingproduct is of the .long oil typeA and rvgives flexible films. The use of one-half this 'qu'a'ntity Example. 17e

5102.9.;gramsfvof the oxyethylatedproduct.de scribedin Example. 5.1512, were Vreaci'1ed1with .35.1 grams of dehydrated fcastor.. fatty :acids` 1- and v:1:31. grams. of -iphthalic anhydride... The materials were heated from 230 -to249 C. yfoi-591A; 'hours to a'curetime ;of..19 seconds andan acid ber oflessthan 10. A-50%ysolution;of ftliisipiodsV uct had avscosityiof more ythan .100i centipoises anda Gardnercolor of 10. ;Theflm-produc'ed from this :productfwa's fast drying,v light 'colored and, hard. .It was of the shortoili'type A l Examplulscl... l I i The resin produced from Example 31a was treated with 116 moleethylene loxide per phenolic hydroxyl. (see table) and reacted .with linseed f atty. acids' and 'succinic anhydride'. v`105 .grams ofthecxyethylated resin, '39.2 grams of inseed fatty acids and f6 grams of the succin'ic rank-ydrid, were heated for Y16 hours at l210 to 24.22. to acure .time of 25secondsand an acidnumber of 5.2. 1A 55% s olutionof `thisesteriiijl product .in x'ylen'ehad a. viscosity .of 110 centipoisesan'd a satisfactory color.v 'Whenthsfsof lution airfdriedy With 0.65%leac l, `0.06% c 1l;ja. l t and 0.02% manganesefintroduced lin 'theiorm of naphthenates, it forrr'i'ed light colored and hard lms. It Was-of the. .medium oil type.

:10 of theDiels-Alderadduct also glves luseful prodv l @ennesima-fromwuichtend 10 bes'mewnat Emmy? '19 harder' E z 15 The ileSYi POduGed from Exemple-185@ WS. mm-p c. oXyeth-ylated with `1.9 moles-of ethylene oxide This example serves to illustrate the effect of 35. per phenolichydroxyl (see table). 107 grains o1 varying' amounts of linseed fatty acids and this oxyethylated material, 33.2 gramslinseed phthalic anhydride on'the para-tertiarylhutyl-l fattyacids, `and 11,'1 grams of adipic acid, were phenol resin from Example la', ox-yethylated heated for 20 hours at 202 to 246 C.to .anacid with any equimolar proportion of ethylene oxide number of 2, yand a hydroxyl number of33. I'he (se'etable). 4The properties andi-conditions'- of 40 xylene solutionof .the; esterified yproduct conreaction are recorded in the following taloleiVV i tain-ing 47.2% solidshada viscosi=ty of ..90 centiuM1221:vv .PL-ms l l. t Hy af FY-' l l s l 1 s. "Temeer: 71111115 Acid 311111 s1. d P11011 o droxyl a-Rsinef -vnt .ity inhyit ma C- @Se y; NO- No.

21 i fACd I- Y 32.3 *60.1" 33.0 f b17.3V l 215-2471; 7% 3.4 '30.0.1r 32. 3 00. 1 23. 0 14. s 205-237 10147 4. 9 51. 2 102.9 75.1 23.0:` 14.2 213-243 17 1.3 74.5 102.9 75.1 29.3V 15.5 219-239 1s 2.0 V7353.-. 32.3 00.1 40.3 12.2 213-240 25 1.9 -47.4 102.9 75.1 29.3 10:3 217-233 1014.V 2.3 172.5 :102.9 V75.1 29.3 18.3 229-233 7. 4.1 67.7 s 1.10219 175.1. 29.3 :23.2 230-242 4% 13.4 49.1 102.9 75.1 @4410 13.1 215-250 4.9 3.3 47.7 '102:9 75.1 53151 112:1 23o-241 17%, 4.5 30.5 `'32.3 V50.1f-` 110.9 227-240 24 3.3 32.3 -00.1 100.4 1 231-241 11,344 1.17 l'9.'0 532:3 500.1 92.5 213-242 .151,4 4.3 11.2.r 32.3 .00.12 74.5 23o-237 19 1.9 14.2- 32.3 00.1 02.3 224-243 1,1912 3.0 v^-15.'19 l .fThe "products have a range ofzpropertiesifcorpoisesV anda yellow color. AIt was of.'refc'iiini'foilt u 60 type.

responding to those observe oil alkyd resins. .Eample 1 6'c s 82:3 grains of theA xyethylated'product of Exf-l ainplef-la, resin oxyethylated Qvvith` an equimt'ilai'fv proportionof ethyleneoxide (seestalole), Were reacted with 12 grams of phthalic "anhydride and 62.8 grams of soybeanfatty acids for 221/2 hours at 233 to 238l C;- to produce an esteried product with an acid number of 4.7. A 49.7% solutipnof. this res-in: had a Gardnerixcolor fofA 12.L Ifhis product, When fcast and air-.driedmrwith (L65 Y'lead 0505 manganese and 10:02:92.- cobalt,l had f2, Ward, hardness "pf` I15.; at-"theend of. 2.4% hour .Itwas o fjthe 'long 'oilgtype'. (The driersi vverewdded.as naphthclates' d in short to long Example 20c ment-vehicle .ratio 'it 'produced' yal satisfactory acidosis -31 Example 1 21o The/.product of Example 82a was oxyethylated with.an equimolar proportion of ethylene oxiderfsee table). 302 grams of a xylene slurry'of this oxyethylated resin were heated with 21, grams of linseed fatty acids and 12.5 grams .of diglycollic acid for 22 hours at 207 to 248v C. to produce aresin of anacid number of 4 and a hydroxyl number of 37.2. A 62% solution of this resinin xylene had a viscosity of y 165 centipoises. Films of this material were baked at A80? C. for'll/z hours with 0.06% cobalt. added as cobalt naphthenate, and were hard and had a good gloss. This was a medium oil resin type.. f vExample 22a i*The resin prepared in Example 56a was oxyethylated with an equimolar proportion of ethylene oxide (see table). 206 grams of this oxyethylated resin, and 105 grams of dimer fatty acids. which consist predominantly of the dimer polymer of linoleic acid, were heated for 22 hoursv at 210 to 240 C. to give a product that had'an acid number under 10 and was soluble in xylene. The product was a dark amber liquid and had a viscosity of 3000 centipoises. This was a resin of the long oil type.

Example 23o 298 grams of the oxyethylated resin used in Example '15c were mixedwith 490 grams of a 50% xylene solution of the Clocker adduct prepared from-heating 200 grams of oleic acid and grams of crotonic acid at 240 to 250 C. for

2 hours.` These materials were heated for 221/2 hours at 208 to 247 C.y A 50% xylene solution of this esteried product was treated with a suitable quantity of metallic driers as-illustratedinfExample 18e and dried to a hard film at room temperature. -These films showed good water and solvent resistance. This was a resin of the long oil type.

Example 24e The resin of Example 57a was oxyethylated in equimolar proportion with ethylene oxide (see table). and 44.8 grams of linseed fatty acids were heated with 21.2 grams of the terpene-maleic acid adduct WW grade (as exemplified by Hercules Pow-v der Company Petrex). The materials were heated to 200 C. to 230 C. for 14 hours until a cure time of 20 seconds was reached. A 50% 32 produced. This product was of the medium oil type.

Example 26e 205 grams of a 58.4% slurry of the oxyethylated product of Example 117a. which had been reacted with 0.85 mole ethylene oxide per mole of resin (see table), were reacted with 24.7 grams of phthalic anhydride and 46.6 grams of linseed fatty acid. The mixture was heated for 7 hours at 200 to 230 C. to a cure time of 20 seconds and an acid number of 6. A solution o! this esteriiied product had a viscosity of 22 centipoises and a very light color. When air-dried with the use of siccatives, films with very pale color and good iiexibility were produced. This was a. prod- 90.5 grams of this oxyethylated resin uct of the long oil type.

Example 27e The product of Example 10a was oxyethylated with 0.75 mole of ethylene oxide per mole of resin (see table). 168.5 grams of a 72.5% slurry of this oxyethylated resin. were mixed with 16.6 grams of phthalic anhydride and 63 grams of linseed fatty acids. The materials were heated for 6 hours at 190 to 225 C. to produce a product having a cure time of 22 seconds, and an acid number of 9.5. A 50% solution in xylene of this esteried product had a viscosity of 80 centipoises and when cast on glass plates and airdried gave films of good flexibility, and moderate film hardness. This was a product of the long oil type.

Example 28e The oxyethylated resin used was the same as that in .Example 27e, preceding. 168.5 grams of a 72.5% slurry of this oxyethylated resin Vwere mixed with 19.8 grams of phthalic anhydride and 37.4 grams of linseed fatty acids. The materials were heated for 71/2 hours at 190 C. to an acid number of 9.3 and a cure time of 12 seconds. A 50% solution of this esteried product had a viscosity of 200 centipoises and satisfactory color.

. 'I'his resin, pigmented or clear, gave fast drying and hard films when air-dried with the usual amounts of siccatives. This product was of the medium oil type.

Eample 29o y The product of Example 10a was reacted with 0.5 mole ethylene oxide so that 50% of the f phenolic hydroxyls were oxyethylated (see table).

solution of this esteried product in xylene had an acid number of 4 and a viscosity of 200 centipoises. Films baked at 150 C. for one hour were hard and had a high gloss. This product was of the long oil type.

Example 25o in 10A hours. Baked at 150 C. without drier, lms

of excellentlcolor, hardness andexibility were 205 grams of a slurry of this partially oxyethylated material, containing 66.4% of solid material. were mixed with 56 grams of linseed fatty acids and 14.7 grams of phthalic anhydride. The material was heated for 27 hours at 210 to 215 C. to produce an esterifled product with a cure time of 50 seconds. and an acid number of 12.4. A 50% solution of this product had a viscosity of 200 centipoises and a Gardner color of 14. The film produced from this solution had excellent air-drying properties and a Sward hardness of medium oil type.

32 after 48 hoursv o'f air-drying. It was of then A' :Example 30e The resin produced from Example 112a was' oxyethylated Withan equimolar proportion or ethylenevoxidelsee table). 318 grams of the 33 for 11/2 hours, gave clear light-colored lms; It was of the medium oil type.

Eaiample 31e Example 32e 4.5 pounds of a 60% xylene solution of the esterified product of Example 7c, were mixed with 2.5 pounds of titanium dioxide, 4 pounds of lithopone, one pound of renedlinseed oil,'0.5 pound of Z-2 bodied linseedoil, 0.5 pound of xylene, 0.1 pound 8% lead naphthenate, .025 pound manganese naphthenate, and .025 pound cobalt naphthenate. These materials, after milling, produced a semi-gloss white paint.

Eazample 33e 102.9 grams of the oxyethylated product used in Example e were mixed with 18.6 grams of phthalic anhydride and 29.3 grams of soybean fatty acids. These materials were heated at 213 to 236 C. for 11 hours to a cure time of 15 seconds and 'anacid number of 3.1. A 48.4% xylene solution of this esteried product had a viscosity of 140 c'entipoises and a Gardner color of 11. This product produced excellent air-drying films which' were exible, hard and very pale. These lms, when subjected to radiation from a carbon arc for 300 hours, showed very slight yellowing. This product was of the short oil type.

Example 34e 102.9 grams of the oxyethylated resin as de-y scribed in Example 15e, were mixed `with 15.5 grams of phthalic anhydride` and 29.3 grams of soybean fatty acids. These materials were heated at 212 to 246 C, for 191A hours to an acid number of 2.4, a hydroxylnumber of 77.4, and a cure time of seconds. A 51.4% solution of this resin in xylene had a vis,cosity ofl 275 lcentip'oises and a Gardner color` lof 12. This material gave lms oi' excellent air-drying and baking properties.

When cast` on glass or tinplate: the esterified product, plus 0.65 lead, 0.05% manganese, and

0.02% cobalt, added as naphthenates, gave air' dry films that hada dust-free time of 8 minutes and a tack-free time of 23 minutes. When baked at 150 C. for one hour with no drier,lms were produced from this material that were very pale, flexible Vand had a Sward hardness of 43 after storage 24.hours at4 100% relative` humidity.'

These same lms, when subjected to radiation with a carbon arc for 300 hours, showed no yellowing or adverse effects. Baked films of this resin, after submersion in 3% sodium hydroxide for three weeks, showed no discoloration or blushing. This resin was ofthe medium oil type.

Example 35e 34 Y seconds. This product had a viscosity of 3,520 centipoises. When baked with a small amount of siccative (0.02% cobalt) it gave a tack-free and print-free lm. This product isof the long oil type.

Example 36e The resin produced in Example 53a was oxyethylated With an equimolar amount of ethylene oxide (see table). 143 grams of this oxyethylated material, 16.7 grams of phthalic anhydride and 56 grams of linseed fatty acids, were heated to 220 to 249 C. for 15 hours to produce an'esteriiied product of low acid number. This resin, when cast and baked, gave lms which were hard and black. It was of a medium oil type.

Example 37e The resin produced in Example 79a was oxyethylated with an equimolar amount of ethylene oxide (see table). 99 grams of this oxyethylated resin, 14.9 grams of phthalic anhydride, and 37.8 grams of dehydrated castor fatty acid lwere heated f or 10 hours at 210 to 245 C. to a cure time of 20 seconds and an acid number of 0.75. This resin was a hard, tack-free solid, with a hydroxyl' number of 50.8. It was of the mediuml oil type.

kExample 38o were heated for ll/hours at 220 to 240 C. to

, .kylated kC14- ''toiC1s-hydrocarbon-substituted'. dif l'75 functional monocyclic monohydricv plienolCia cure time of 19 seconds, an acid number of 5.5, and a hydroxyl number of^34.'6. `This esteried product, when pigmentedwith'titanium dioxide at a vehicle-pigment-ratio of 1:1, produced an Yexcellent hig'hgloss, fast-drying white enamel.

It Was of the medium oil'type.

In the foregoing examples, the fact that a catalyst might-.be used in the esterication step was not'illustra'ted. Catalysts, such as. sulfuric acid, organic sulfo acids, litharge, and metallic carbonates, are infrequently used and vmight be used, but with lsubsequent effect on colorof the final product.

The foregoing examples, 1c through 38e, illustrate the preparation of useful llm-forming'esterication products from a number of the oxyalkylated 1 resins previously described. Similar esterifcationprocedures, using the fatty acids of dryingV or semi-drying oils and, advantageously, a dicarboxy acid, applied to any, of the oXyalkylated derivatives illustrated inExamples 1b through 5b and in -the oxyethylation'table, give useful products, varying in properties from those characteristic of the short oil type of product to those characteristic of the long oil type of product. In general, these are compatible with drying oils and so may be used as constituents of paints; and by themselves, `when used with suitablesolvents, they form useful varnishes which,`

on the incorporation ofupigments, form useful enamels. Ingeneral, in use, the products'willbe employed along Withappropriate siccatives in the usual way. y y y. This application 'is in part a continuation of applications, Serialv Nos. 751,624, filed May. 31, 1947, 518,660, 518,661, and 518,662, .filed January 17, 1944, allhofwhicfh are now abandoned. "We'blaim: Y f' Q 'esterication product of (l) an ,oxyalacidosis to Cia-aldehyde resin in which the C4.. to Cissubstitutent is in one of the positions, ortho and para, of the phenol and in which the aldehyde is one which has but one functional group reactive With said phenol in which the ratio of oxyalkylene groups to phenolic nuclei is from less than 2:1 to about 0.5:l,` and the alkylene radie cals of the oxyalkylene groups are those of alpha, beta-alkylene oxides and are selected from the class consisting of ethylene, propylene, butylene, hydroxypropylene and hydroxybutylene radicals, and the oxyalkylene groups are linked to the phenolic nuclei at the 1-position, and I( 2) the fatty acids of an oil of the class consisting of dryingA and semi-drying oils in amount at least 20% based stoichiometrically on the total hydroxyl content of the oxyalkylated resin; with the proviso that at least 50% stoichiometrically of the total hydroxyl content of the oxyalkylated resin is esteriied by a material of the class consisting of such fatty acids and polycarboxy acids, with the proviso that the polycarboxy acid contains only oxygen, hydrogen and carbon and in amount does not exceed 70% based stoichiometrically on the total hydroxyl content of the oxyalkylated resin.

2. An esterication product of (1) an oxyalkylated C4 to C1a-hydrocarbon-substituted difunctional monocyclic monohydric phenol-Cito Cra-aldehyde resin in which the C4- to Ciasubstitutent is in one of the positions, ortho and para, of the phenol and in which the aldehyde is one which has but one functional group reactive with said phenol in which the ratio of cxyalkylene groups to phenolic nuclei is from less than 2:1 to about 0.5:1, and the alkylene radicals of the oxyalkylene groups are those of alpha,betaalkylene oxides and are selected from the class consisting of ethylene, propylene, butylene, hydroxypropylene and hydroxybutylene radicals, and the oxyalkylene groups are linked to the phenolic nuclei at the l-position; (.2) the fatty acids of an oil of the class consisting of drying and semi-drying oils in amount at least 20% based stoichiometrically on the total hydroxyl content of the oxyalkylated resin; and (3) a dicarboxy acid in amount not exceeding 70% based stoichiometrically on the total hydroxyl content ofthe oxyalkylated resin; with the proviso that at least 50% stoichiometrically of the` total hydroxyl content of the oxyalkylated resin is esteried by a material of the class consisting of such fatty acids and dicarboxy acids, and the proviso that the dicarboxy acid contains only carbon, hydrogen and oxygen.

3. An esterication product of (.1) an oxyalkylated C4- to Cia-hydrocarbon-substituted difunctional monocyclic monohydric phenol-Clto Caz-aldehyde resin in which theC4.. to Cissubstituent is in one of the positions, ortho and para, of the phenol and in which the aldehyde is one which has but one functional groupref active with said phenol in Which the ratio of oxyalkylene groups to phenolic nuclei is from less than 2:1 to about 0.5 1, and the alkylene radicals of the oxyalkylene groups are those of alpha,

beta-alkylene oxides and are selected from the.

class consisting of ethylene, propylene, butylene, hydroxypropylene and hydroxybutylene radicals, and the oxyalkylene groups are'4 linked to the phenolic nuclei at the 1position; (2) the fatty acids of an oil of the class consisting of drying and semi-drying oils in amount at least 20% based stoichiometrically on the total hydroxyl content of the oxyalkylated resin; and (3) phthalic acid in y amount not yexceeding '70% based'stoichiometrically on the total hydroxyl content of the oxyallrylatedv resin; with the proviso that at least 50% stoichiometrically of the total hydroxyl content of the oxyalkylated vresin is esteried by a material of the class consisting of such fatty acids and phthalic acid.

4. An esterication product of (1) an oxyalf kylation product of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide,l and (B) an. oxyalkylation-f susceptible, fusible, organic solvent-soluble, Water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenolr and an aldehyde having not over 8 carbon atoms and having one carboxyl group reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; vsaid phenol being of the formula in which R. is a hydrocarbon radical having at.

least 4 and not more than 18 carbon atoms and substituted in one of the positions, ortho and para; said oxyalkylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyl groups of a plurality of divalent radicals having the formula R10 in which R1 is a member selected from the class COIlSStillg of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, with the proviso that from about one-half to less than 2 y moles of alkylene oxide be introduced for each phenolic nucleus; and (2) the fatty acids of an oil of the class consisting of drying and semidrying oils in amount at least 20% based stoichiometrically on the total hydroxyl content of the oxyalkylated resin; with the proviso that at least 50% stoichiometrically of the total hydroxyl content of the oxyalkylated resin is esteried by a material of the class consisting of such fatty acids and polycarboxy acids, with the proviso that` the polycarboxy acid contains only oxygen, hydrogen and carbon and in amount does not exceed 70% based stoichiometrically on the total hydroxyl content of the oxyalkylated resin.

5. An esteriiication product of (1) an oxya1' kylation product of-'(A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycidev and methylglycide, and (B) an oxyalkylationsusceptible, fusible, organic solvent-soluble, Iwater-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one carboxyl group .reactive toward said phenol; said resinI being formed in the substantial absence' of phenols of functionality greater than two; said' phenol being of the formula least 4 and not more than y18 carbon atoms and substituted in one of the positions, orthov and para; :said oxyallylated resin being characterized by the vintroduction into the resin molecule at the phenolic hydroxyl groups of a, plurality of divalent radicals having the formula R1O in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, with the proviso that from about one-half to less than 2 moles of alkylene oxide be introduced for each phenolic nucleus; (2) the fatty acids of an oil of the class consisting of -drying and semi-drying oils in amount at least based stoichiometrically on the total hydroxyl content of the oxyalkylated resin; and (3) a dicarboxy acid in amount not exceeding 70% based stoichiometrically on'the total hydroxyl vcontent of the oxyalkylated resin; with the proviso that at least 50% stoichiometrically ofthe total hydroxyl content ofl the oxyalkylated resin is esteried by a material of the class consisting of such fatty acids and dicarboxy acids, and the proviso that the. dicarboxy acid contains only carbon, hydrogen and oxygen.

6.1An esterication product of (l) an oxyalkylation Product of (A) Van alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (B) anoxyalkylationsusceptible, fusible, rorganic solvent-soluble, Water-insoluble phenol-faldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol'and-an aldehyde having not over 8 carbon atoms and having one carbonyl group reactive toward said phenol; said resin being formedy in the substantial absence of phenols of functionalityv greater thany two; said phenol being of the formula. Y Y i A-on in which R is a hydrocarbon radical havingat consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals,',a nd hydroxybutylene radicals, with the proviso that from about onen-half to lessathan2 moles of alkylene oxide be introduced for eachphenolic nucleus; (2) the fattyacids of an oil ofthe-class consistingof dryingand semi-drying oilsfin amount at least 20%A based stoichiometrically onthe total hydroxyl content of the oxy-v alkylated resin; `and (3) phthalic acid in .amount not'exceeding 70%. based stoichiornetrically` onv the@ total hydroxyl content of the oxyalkylated resin; with the proviso` that at least 50% stoichiometrically-ofathe total hydroxyl content of theaoxyalkylated resinV is "esteried by a material oflltheclass Aconsisting of Vsuchfatty acids tand vent-soluble, Ilow-stage, acid-catalyzed -phenolfformaldehyde resin; said resin being` derived ,by reaction between a; ,difunctional monohydric phenol and formaldehyde;` saidresin f being formed inthe substantial absence of phenols of functionality greater than two; said phenol being of the vformula y y onv in which R is a hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in one of the positions, ortho and para ;v said oxyethylated resinbeingcharacteri'zed by the j introduction into the resin molecule at the phenolic hydroxyl groups of 4a plurality of divalent radicals having the formula 02H40, with the proviso that from about one-#half to less than 2 molesl of ethylene oxide beintroducedfor each phenolic nucleus; andf-(Z) 'the fatty. acids'cf an oil of' the class"y consisting of drying 'andjsem'ie drying oils in amount at leastl20% basedstoi chiometricallyv on the total hydroxylfcontentfof the oxyethylated resin; withjthe proviso that at least 50% 'stoichiometrically of the total hydroxyl contentv of the oxyethylated resinisesteried by a material of the class consisting of SuchIatty acids'and polycarboxy acids, with the proviso that1 the polycarboxy acid contains vonly Oxygen. .hydrogen and carbon and in amountdoes not ex-l ceed '70% based stoichiometrically on thetotal hydroxyl content of the oxyethylated resin.` 1

- 8.r An esterication product of (1) an joxye'thr ylation product of (A) ethylene oxide and (B) an oxyethylationesusceptible, fusible,l organic sol: vent-soluble, low-stage, acid-catalyzed phenol-v formaldehyde resin; said Aresin beingderived byl reaction between a difunctional monohydric phenol @and formaldehyde; saidA resin "being formedY inthe substantial absence ofQphenols of functionality greater than two; said of the" formula f in which R is a hydrocarbon radical having at least Ltand not-more than18 carbon atoms and' substituted in one.` of the positions, ortho and para; said oxyethylated resinbeing characterized'- bythe,introdution into. the resin molecule-at the. phenolic hydroxyl groups Lof, a, plurality lof divalent radicalshavingthe formula C2H4O,fwith the proviso that from aboutone-half to less, than' 2 moles of ethylene oxide be introduced for each phenolic nucleus;- (2) the fatty acids of; an oilof the class consisting `of drying and` semi-drying;

oilsy in amount-atleast 20% basedstoichiometrically on the total hydroxyl content of the oxyethylated resin; and (3) a dicarboxy acid-yin amount. vnot exceedingf |70% based stoichiometand oxygen.

ylation product of (A) ethylene oxide and (B) an oxyethylation-susceptible, fusible, organic solvent-soluble, low-stage, acid-catalyzed phenolformaldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol land formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in one of the positions, ortho and para; said oxyethylated resin being characterized by ,the introduction into the resin molecule at thephenolic hydroxyl groups of a plurality of divalent radicals having the formula` 02H40, with the proviso that from about one-half to less than 2 moles of ethylene oxide be introduced for each phenolic nucleus; (2) the fatty acids of an oil of the-classconsisting of drying and semi-drying oils'inamount at least 20% based stoichiometrically on the total hydroxyl content of the oxyethylated resin; and (3) phthalic acid in amount not exceeding 70% based stoichiometrically on the` total hydroxyl content of the oxyethylated resin; with the provisothat at least 50% stoichiometrically of the total hydroxyl content of thev oxyethylated resin is esteried by a material of the class consisting of such fatty acids and phthalic acid.

`10. An esteriflcation product of (1) an oxyethylation yproduct of (A) ethylene oxide and (B) an oxyethylation-susceptible, fusible, organic solvent-soluble, low-stage. acid-catalyzed phenolformaldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol andv formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula irl-which R. is an aliphatic hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in the para position; said oxyethylated resin being characterized by the introduction -into the resin molecule'at the phenolichydroxyl groupsof a plurality of divalent radicalshaving vtheformula C21-140, with the proviso'that one mole ofethylene oxide be introduced for each phenolic nucleus; and (2) the fatty acids of an oil of the class consisting of drying and semi-drying oils in amount at least 20% based stoichiometrically on the total hydroxylA content of the oxyethylated resin; with ther-proviso that'at' least 50% stoichiometrically of -the total' hydroxyl content of the oxyethylated resin. is esteriedby a material of the class consisting of such fatty acids and polycarboxy acids, withlthe proviso that the polycarboxy acid contans-lonly oxygen, hydrogen and carbon and in amount ldoes'not exceedA '10% based stoichiometrically on the total hydroxyl content of the oxyethylated resin. c

v`11;;An estercation product of (l) an oxyeth- 40 ylation product of (A) ethylene oxide and (B) an oxyethylation-susceptible, fusible, organic solvent-soluble, low-stage, acid-catalyzed phenolformaldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in the para position; said oxyethylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyl groups of a plurality of divalent radicals having the formula CzHlO, with the proviso that one mole of ethylene oxide be introduced for each phenolic nucleus; (2) the fatty acids of an oil of the class consisting of drying and semi-drying oils in amount at least 20% based stoichiometricallyon the total hydroxyl content of the oxyethylated resin; and (3) a dicarboxy acid in amount not exceeding based stoichiometrically on the total hydroxyl content of the oxyethylated resin; with the proviso that at least 50% stoichiometrically of the total hydroxyl content of the oxyethylated resin is esteried by a material of the class consisting of such fatty acids and dicarboxy acids, and the proviso that the dicarboxy acid contains only carbon, hydrogen and oxygen.

l2. An esterication product of 1) an oxyethylation product of (A) ethylene oxide and (B) an oxyethylation-susceptible, fusible, organic solvent-soluble, low-stage, acid-catalyzed phenolformaldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in the para position; said oxyethylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyl groups of a plurality of divalent radicals having the formula C2H4O, with the proviso that one mole of ethylene oxide be introduced for each phenolic nucleus; (2) the fatty acids of an oil of the class consisting of drying and semi-drying oils in amount at least 20% based stoichiometrically on the total hydroxyl content of the oxyethylated resin; and (3) phthalic acid in amount not exceeding 70% based stoichiometrically on the total hydroxyl content of the oxyethylated resin; with the proviso that at least 50% stoichiometrically of the total hydroxyl content of the oxyethylated resin'is esterifiedby a materialof the class consisting of such` fatty acids andphthalic acid.

413. An esterincauon product of (1) an oxyeth- 

1. AN ESTERIFACTION PRODUCT OF (1) AN OXYALKYLATED C4- TO C18-HYDROCARBON-SUBSTITUTED DIFUNCTIONAL MONOCYCLIC MONOHYDRIC PHENOL-C1TO C8-ALDEHYDE RESIN IN WHICH THE C4-TO C18SUBSTITUTENT IS IN ONE OF THE POSITIONS, ORTHO AND PARA OF THE PHENOL AND IN WHICH THE ALDEHYDE IS ONE WHICH HAS BUT ONE FUNCTIONAL GROUP REACTIVE WITH SAID PHENOL IN WHICH THE RATIO OF OXYALKYLENE GROUPS TO PHENOLIC NUCLEI IS FROM LESS THAN 2:1 TO ABOUT 0.5:1, AND THE ALKYLENE RADICALS OF THE OXYALKYLENE GROUPS ARE THOSE OF ALPHA, BETA-ALKYLENE OXIDES AND ARE SELECTED FROM THE CLASS CONSISTING OF ETHYLENE, PROPYLENE, BUTYLENE, HYDROXYPROPYLENE AND HYDROXYBUTYLENE RADICALS, AND THE OXYALKYLENE GROUPS ARE LINKED TO THE PHENOLIC NUCLEI AT THE 1-POSITION, AND (2) THE FATTY, ACIDS OF AN OIL OF THE CLASS CONSISTING OF DRYING AND SEMI-DRYING OILS IN AMOUNT AT LEAST 20% BASED STOICHIOMETRICALLY ON THE TOTAL HYDROXYL CONTENT OF THE OXYALKYLATED RESIN; WITH THE PROVISO THAT AT LEAST 50% STOICHIOMETRICALLY OF THE TOTAL HYDROXYL CONTENT OF THE OXYALKYLATED RESIN IS ESTERIFED BY A MATERIAL OF THE CLASS CONSISTING OF SUCH FATTY ACIDS AND POLCARBOXY ACID CONTAINS THE PROVISO THAT THE POLYCARBOXY ACID CONTAINS ONLY OXYGEN, HYDROGEN AND CARBON AND IN AMOUNT DOES NOT EXCEED 70% BASED STOICHIOMETHRICALLY ON THE TOTAL HYDROXYL CONTENT OF THE OXYALKYLATED RESIN. 